EP3394007A1 - Composition d'engrais à base de nitrate d'ammonium, et son procédé de fabrication - Google Patents

Composition d'engrais à base de nitrate d'ammonium, et son procédé de fabrication

Info

Publication number
EP3394007A1
EP3394007A1 EP16819069.2A EP16819069A EP3394007A1 EP 3394007 A1 EP3394007 A1 EP 3394007A1 EP 16819069 A EP16819069 A EP 16819069A EP 3394007 A1 EP3394007 A1 EP 3394007A1
Authority
EP
European Patent Office
Prior art keywords
additive
stabilizing
fertilizer composition
ammonium nitrate
passivation layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP16819069.2A
Other languages
German (de)
English (en)
Inventor
Francois Ledoux
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yara International ASA
Original Assignee
Yara International ASA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yara International ASA filed Critical Yara International ASA
Publication of EP3394007A1 publication Critical patent/EP3394007A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C1/00—Ammonium nitrate fertilisers
    • C05C1/02—Granulation; Pelletisation; Stabilisation; Colouring
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/18—Nitrates of ammonium
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00—Fertilisers characterised by their form
    • C05G5/30—Layered or coated, e.g. dust-preventing coatings
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00—Fertilisers characterised by their form
    • C05G5/40—Fertilisers incorporated into a matrix
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/78—Compounds containing aluminium, with or without oxygen or hydrogen, and containing two or more other elements
    • C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
    • C01F7/785—Hydrotalcite

Definitions

  • the instant disclosure relates to fertilizer compositions and methods of making and using the same. More specifically, the instant disclosure relates to blast suppressant and/or blast resistant ammonium nitrate fertilizer compositions, as well as methods of making and using the same.
  • Ammonium Nitrate (AN) fertilizer, combined with fuel oil (ANFO) or other fuels is a common explosive used throughout the world.
  • ANFO fuel oil
  • malicious parties e.g. terrorists
  • explosives i.e. bombs and improvised explosive devices.
  • WO2015/073561 describes a class of additives that can be added to AN fertilizers, also referred to therein as "stabilizer material” that reduces, prevents or eliminates the AN fertilizer from being used as an ANFO-type explosive.
  • Suitable stabilizer materials include a layered double hydroxide (LDH), apatite and combinations thereof. Preferred LDH compounds are listed as hydrotalcite and hydrocalumite and a preferred apatite is mentioned as hydroxyapatite.
  • Additives may be incorporated within AN fertilizers to impart desirable characteristics on the AN fertilizer.
  • additives may be used as a stabilizing additive to reduce, prevent, or eliminate the potential for the AN fertilizer to be sued as an ANFO-type explosive.
  • such additives can react with the AN fertilizer. This is particularly the case where such additives contain carbonates, oxides, hydroxides, contain water of hydration or water locked within the structure (e.g. within an interlayer substructure).
  • a fertilizer composition comprising an ammonium nitrate material; an additive wherein the additive contains at least one carbonate, oxide, hydroxide, water of hydration, or water locked within the additive; wherein the additive further comprises a passivation layer.
  • the additive is a stabilizing additive.
  • the additive is a layered double hydroxide or an apatite. More particularly, the additive is hydrocalumite, hydrotalcite, or hydroxyapatite.
  • the additive is at least 12.5 wt% of the total fertilizer composition.
  • the passivation layer is substantially non-reactive with the ammonium nitrate material.
  • the passivation layer may substantially cover the surface of the additive.
  • the passivation layer comprises at least one of calcium sulfate, calcium phosphate, magnesium sulfate, magnesium phosphate, or calcium fluoride.
  • a method is provided of making a fertilizer composition comprising providing an ammonium nitrate material; adding a mobile additive to the ammonium nitrate material; and adding a stabilizing additive to the ammonium nitrate material containing the mobile additive.
  • the mobile additive is sulphuric acid, ammonium bisulfate, ammonium sulfate, aluminum sulfate, phosphoric acid, monoammonium phosphate, diammonium phosphate, hydrogen fluoride, fluorosilicic acid, or the like
  • the stabilizing additive is a layered double hydroxide or an apatite.
  • the stabilizing additive may be hydrocalumite, hydrotalcite, or hydroxyapatite.
  • the mobile additive is less than 15 wt% of the ammonium nitrate material. In more particular embodiments, the mobile additive is from l-10wt% of the ammonium nitrate material, 2-5 wt% of the ammonium nitrate material, or 3-5 wt% of the ammonium nitrate material.
  • the stabilizing additive is at least 12.5 wt% of the total fertilizer composition. More particularly, the stabilizing additive is at least 12.5 wt% to not greater than 20wt% of the total fertilizer composition.
  • a method comprising forming a passivation layer on a stabilizing additive; and adding the stabilizing additive with the passivation layer to an ammonium nitrate material.
  • additives to stabilize the explosive potential of AN fertilizers are desirable, however, such additives can react with the AN fertilizer. This is particularly the case where such stabilizing additives contain carbonates, oxides, hydroxides, contain water of hydration or water locked within the structure (e.g. within an interlayer substructure).
  • a reaction between the AN fertilizer and a metal oxide could proceed according to:
  • any released water may affect the consistency or storability of the fertilizer, or the ability of the additive to stabilize the explosive potential of AN fertilizers.
  • the metal nitrate may be soluble within the AN melt.
  • the metal nitrate may be soluble within the AN melt.
  • calcium nitrate or magnesium nitrate would be soluble within the AN melt.
  • Reactive additives can be protected from the bulk AN through the formation of a substantially non-reactive passivation layer on the surface of the additive.
  • the passivation layer may be formed on the additive either prior to being added to the AN fertilizer or it can be formed in situ within the AN melt in which case, some minor reaction may still occur with the AN, in competition with the formation of the passivation layer.
  • the passivation layer is formed in situ within the AN melt.
  • a mobile ion such as sulfate, phosphate or fluoride may be added to the AN melt prior to addition of the additive.
  • the mobile ion may be added to the AN melt in the form of a mobile additive.
  • a mobile additive would be as sulfuric acid, ammonium bisulfate, ammonium sulfate (AS), aluminum sulfate, phosphoric acid, monoammonium phosphate (MAP), diammonium phosphate (DAP), hydrogen fluoride (HF), fluorosilicic acid, or the like.
  • the AN melt may contain less than 15wt% of mobile additive, less than 10wt% of mobile additive, from l-10wt% of mobile additive, from 2-7wt% of mobile additive, from 2-5wt% of mobile additive, from 3-5wt% of mobile additive.
  • the amount of mobile ion added to the AN melt needs to greatly exceed the stoichiometric amount needed to cover the full surface of the additive, taking into account the steric and spatial occupation of the molecules forming the passivation layer.
  • the mobile additive while soluble within the AN melt, can react with the surface of the additive to form a passivation layer to protect the bulk of the additive and to prevent, reduce, or eliminate the ability of the stabilizing additive from reacting with the AN melt.
  • a passivation layer may form comprising calcium sulfate, calcium phosphate, magnesium sulfate, magnesium phosphate, calcium fluoride, as the case may be and depending on the nature of the mobile ion.
  • Such passivation layers are preferably substantially non-reactive and substantially insoluble within the AN melt.
  • the additive may be impregnated prior to addition to the AN melt.
  • a calcium or magnesium nitrate may be used to impregnate the additive.
  • the impregnation material may react with the mobile ion to form the passivation layer on the surface of the additive.
  • a passivation layer is formed on the surface of the additive prior to being added to the AN melt.
  • the passivation layer may alternatively comprise a non-reactive coating applied to the additive.
  • layered double hydroxide means: a class of compounds which are characterized by multiple (e.g. two) positively charged layers and weakly bound, often exchangeable central ion(s) (e.g. negatively charged ions) located in the interlayer (middle) region.
  • LDHs are commonly referred to by the following generic chemical formula: [M 2+ i- x M 3+ x(OH)2] q+ (X n -) q /n-*yH 2 0 (2)
  • Non-limiting examples of LDH compounds include: hydrotalcites, hydrocalumite, hydromagnesite, takovite, woolite, and combinations thereof.
  • intercalated means: a substances which has another substance or material inserted between or among existing elements or layers.
  • an LDH is intercalated with its central/interlayer region being replaced with other anions or compounds.
  • Non-limiting examples of intercalated LDH include: herbicides, pesticides, anti-fungal agents, supplemental nutrients (e.g. phosphorous compounds, nitrogen compounds, sulfur compounds, trace- element compounds, and combinations thereof).
  • the LDH is intercalated with a nitrate.
  • the LDH is intercalated with a sulfate.
  • the LDH is intercalated with a phosphate.
  • LDH comprises hydrotalcite (HTC). In some embodiments, LDH comprises hydrocalumite.
  • hydrotalcite means: a layered double hydroxide of the following formula:
  • Non-limiting examples of groups of materials within the hydrotalcites supergroup include: hydrotalcites group, quintinite group, fougerite group, woodwardite group, glaucerinite group, cualstibite group, hydrocalumite group, and unclassified.
  • hydrotalcites include: pyroaurite, stichtite, meixnerite, iowaite, droninoite, woodallite, desaurelsite, takovite, reevesite, jamborite, quintinite, charmarite, caresite, zaccagnaite, chrlomagaluminite, fougerite, woodward ite, zincowoodwardite, honessite, claucocerinite, hydrowoodwardite, carrboydite, hydrohonessite, mountkeithite, sincaluminite, wasmlandite, shigaite, nikischerite, motukoreaite, natroglaucocerinite, karchevskyite, cualstibite, xincalstibite, hydroclumite, kuzelite, coalingite, brugnatellite, muskoxite, and combinations thereof.
  • Non-limiting examples of intercalated hydrotalcites include: HTC-carbonate, HTC-phosphate, HTC-nitrate, and combinations thereof.
  • apatite means: a phosphate mineral having calcium phosphate with some fluorine, chlorine, and other elements. In some embodiments, apatite is neutralized with group of phosphate minerals.
  • apatite compound is hydroxyapatite.
  • first to second stabilizing additives are as follows: 2 wt.
  • first to second stabilizing additives are as follows: 5 wt. % of a first and 10 wt. % of a second, 7.5 wt. % of each of the first and the second.
  • the content of first to second stabilizing additives are as follows: 5 wt. % of a first and 15 wt. % of a second, or 10 wt. % of each of the first and the second.
  • the content of first to second stabilizing additives are as follows: 5 wt. % of a first and 20 wt, % of a second, 10 wt. % of a first and 15 wt, % of a second; 12.5 wt % of each of the first and the second.
  • first to second stabilizing additives are as follows: 5 wt. % of a first and 25 wt. % of a second, 10 wt, % of a first and 20 wt. % of a second; 15 wt. % of each of a first and second.
  • AN-type explosive means: ammonium nitrate-based fuel explosives, where fuels include fuel oil (ANFO-type explosives) or other fuels like powdered sugar or aluminum powder.
  • fertilizer means: a substance used to make soil more fertile.
  • a fertilizer includes ammonium nitrate.
  • fertilizer is ammonium nitrate fertilizer which includes at least one stabilizing additive, where the stabilizing additive has a passivation layer.
  • the fertilizer composition of the instant disclosure is in a single form (i.e. pellets, prills, granules, disks, or powder). In some embodiments, the fertilizer composition of the instant disclosure is in multiple forms (i.e. a mixture of two or more forms, including pellets, pastilles, flakes, prills, granules, disks, or powder).
  • the fertilizer composition comprises: a mesh size of 4, a mesh size of 6, a mesh size of 8, a mesh size of 10, a mesh size of 12, a mesh size of 14, a mesh size of 16, a mesh size of 18, or a mesh size of 20.
  • the fertilizer composition comprises: a mesh size of 20, a mesh size of 30, a mesh size of 40, a mesh size of 50, a mesh size of 60, a mesh size of 70, a mesh size of 80, a mesh size of 90, or a mesh size of 100. In some embodiments, the fertilizer composition comprises a
  • the fertilizer composition comprises a
  • the fertilizer compositions include: uncoated materials, coated materials, and/or multi-coated materials (i.e. more than one coating).
  • a stabilizing additive in accordance with the instant disclosure causes blast suppression and/or a desensitization of the resulting fertilizer composition.
  • ammonium nitrate material (also interchangeably referred to as AN) means: a composition including ammonium nitrate (NH 4 N0 3 ).
  • ammonium nitrate is used in agriculture as a high- nitrogen fertilizer, though AN fertilizer can also be used as an oxidizing agent in explosives (e.g. including improved explosive devices).
  • stabilizing additive means: a material added to another material to prevent or retard an unwanted alteration of physical state.
  • a stabilizing additive is present with an ammonium nitrate material to provide a fertilizer composition which prevents or retards an unwanted oxidation/explosion of the composition.
  • the stabilizing additive comprises an additive.
  • additive means: a substance added to another in defined amounts to effect a desired change in one or more properties.
  • a “stabilizing additive” is added to a fertilizer comprising ammonium nitrate in order to prevent, reduce, or eliminate the ability of the composition to be utilized as a material (e.g.
  • a “mobile additive” is added to the fertilizer to form a passivation layer in situ on the stabilizing additive in order to prevent, reduce or eliminate the ability of the stabilizing additive to react with the nitrate fertilizer.
  • a "passivation layer” means a protective surface layer that is substantially non-reactive. All references to a stabilizing additive herein, unless otherwise indicated, refer to such a stabilizing additive comprising a passivation layer.
  • the fertilizer composition comprises: at least 5 wt. % stabilizing additive; at least 7 wt. % stabilizing additive; at least 10 wt. % of stabilizing additive; at least 12.5 wt.% of stabilizing additive at least 15 wt. % of stabilizing additive; at least 20 wt. % of stabilizing additive; at least 25 wt. % of stabilizing additive; at least 30 wt. % of stabilizing additive; at least 35 wt. % of stabilizing additive; at least 40 wt. % of stabilizing additive; at least 45 wt. % of stabilizing additive; or at least 50 wt. % of stabilizing additive.
  • the fertilizer composition comprises: not greater than 5 wt. % of stabilizing additive; not greater than 7 wt. % of stabilizing additive; not greater than 10 wt. % of stabilizing additive; not greater than 15 wt. % of stabilizing additive; not greater than 20 wt. % of stabilizing additive; not greater than 25 wt. % of stabilizing additive; not greater than 30 wt. % of stabilizing additive; not greater than 35 wt. % of stabilizing additive; not greater than 40 wt. % of stabilizing additive; not greater than 45 wt. % of stabilizing additive; or not greater than 50 wt. % of stabilizing additive.
  • the fertilizer composition comprises a stabilizing additive in the form of particles having a volume based average particle size (d50) in the range of 0.1 to 500 ⁇ as measured by conventional laser diffraction methods.
  • the stabilizing additive may also have an average particle size (d50) in the range of 1 to 250 ⁇ .
  • the stabilizing additive may also have an average particle size (d50) in the range of 5 to 100 ⁇ .
  • the stabilizing additive in the form of solid particles having a volume based average particle size (d50) in the range of 0.1 to 500 ⁇ , is mixed into an AN melt, it is possible to obtain fertilizer particles comprising a stabilized additive heterogeneously or homogeneously distributed in the AN.
  • AN particles comprising stabilizing additives in the coating only may not stabilize the explosive potential equally good.
  • a solid fertilizer particle with a diameter in the range of 1 to 10 mm comprising more than 70% w/w AN and a solid stabilizing additive which is homogeneously distributed in the AN, wherein the stabilizing additive comprises a passivation layer substantially covering the surface of the stabilizing additive.
  • explosive device means: a device that provides for a sudden, loud, and violent release of energy that happens when the device (or material therein) breaks apart in such a way that sends parts flying outward.
  • Non-limiting examples of explosive devices include bombs and/or improvised explosive devices.
  • stabilizing additives of the instant disclosure effect a reduction in or elimination of the detonation of ammonium nitrate material (e.g. utilized in an explosive device as an oxidizing material).
  • suppressant means: an agent that tends to prevent, control, or reduce the intensity of a particular property of a material.
  • suppressant effects are quantified by measuring a reduction in specific impulse of a fertilizer composition, as compared to control
  • suppressant refers to a chemical mechanism of blast inhibition and/or prevention.
  • diluting agent means: a diluting agent.
  • the stabilizing additives to the ammonium nitrate act as filler, thinning out the proximity of particles of ammonium nitrate from one another.
  • diluent refers to a mechanical mechanism of blast inhibition and/or prevention (i.e. dilution by addition of stabilizing additives which acts as a filler material).
  • substantially non-reactive means: dimensionally stable.
  • substantially non-reactive means inert (non- reacting).
  • substantially non-reactive stabilizing additives include: sand, clay (i.e. naturally occurring and/or synthetic clays), aggregate (i.e. rocks), and the like.
  • the fertilizer composition includes a pH adjusting components.
  • pH adjusting components include: nitric acid, phosphoric acid, bauxite residue, ammonia, dolomite, etc.
  • the fertilizer composition includes a plant nutrient.
  • plant nutrients include: N, P, K, Mg, Ca, S, trace elements (Fe, Mn, metals present in the stabilizing additive compounds), and combinations thereof.
  • UltraCarb from LKAB Minerals was used as an additive which is a combination of huntite and hydromagnesite.
  • Huntite is a carbonate mineral with the chemical formula Mg3Ca(C03) 4 and hydromagnesite is an LDH, specifically a hydrated magnesium carbonate mineral with the formula Mg 5 (C03) 4 (OH)2-4H20.
  • Example 1 50g of additive (UltraCarb) was added to 200g AN and 2g H 2 0 at 180°C. Significant foaming was immediately observed and the reaction stopped after 8 minutes.
  • Example 2 50g of additive (UltraCarb) was added to 200g AN and 2g H 2 0 at 180°C. Significant foaming was immediately observed and the reaction stopped after 8 minutes.
  • Example 2 50g of additive (UltraCarb) was added to 200g AN and 2g H 2 0 at 180°C. Significant foaming was immediately observed and the reaction stopped after 8 minutes.
  • additive UltraCarb

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Inorganic Chemistry (AREA)
  • Fertilizers (AREA)

Abstract

Selon la présente invention, des additifs peuvent être ajoutés à des engrais afin de conférer des caractéristiques souhaitables. Par exemple, une classe d'additifs souhaitables a été découverte qui stabilise le potentiel explosif des engrais à base d'AN, toutefois, ces additifs peuvent réagir avec l'engrais à base d'AN lors de sa fabrication ou pendant son stockage. C'est notamment le cas lorsque les additifs contiennent des carbonates, des oxydes, des hydroxydes, contiennent de l'eau d'hydratation ou de l'eau bloquée dans la structure (par exemple, dans une sous-structure inter-couche). Cette réaction peut être évitée si l'additif présente une couche de passivation recouvrant sensiblement la surface de l'additif. La couche de passivation étant sensiblement non réactive et sensiblement insoluble, protège l'additif de sorte que l'additif conserve ses propriétés souhaitées et l'engrais conserve sa qualité. Selon d'autres aspects, l'invention concerne des procédés de fabrication de cet engrais.
EP16819069.2A 2015-12-21 2016-12-20 Composition d'engrais à base de nitrate d'ammonium, et son procédé de fabrication Withdrawn EP3394007A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NO20151761 2015-12-21
PCT/EP2016/081940 WO2017108801A1 (fr) 2015-12-21 2016-12-20 Composition d'engrais à base de nitrate d'ammonium, et son procédé de fabrication

Publications (1)

Publication Number Publication Date
EP3394007A1 true EP3394007A1 (fr) 2018-10-31

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EP16819069.2A Withdrawn EP3394007A1 (fr) 2015-12-21 2016-12-20 Composition d'engrais à base de nitrate d'ammonium, et son procédé de fabrication

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US (1) US20180370864A1 (fr)
EP (1) EP3394007A1 (fr)
CN (1) CN108698948A (fr)
CO (1) CO2018007547A2 (fr)
WO (1) WO2017108801A1 (fr)

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CN115991618A (zh) 2017-05-17 2023-04-21 沙特基础工业全球技术公司 抗结块肥料组合物
US12110258B2 (en) 2018-11-20 2024-10-08 SABIC Agri-Nutrients Company Coated fertilizer containing urease inhibitor
BR112021011301A2 (pt) 2018-12-11 2021-08-31 Sabic Global Technologies B.V. Grânulo de fertilizante ácido sólido, mistura de fertilizante ou um fertilizante composto, e, métodos para fertigação e para fabricar o grânulo de fertilizante ácido sólido
WO2020168386A1 (fr) * 2019-02-22 2020-08-27 Alcoa Of Australia Limited Composition d'engrais
AU2024274892A1 (en) 2023-05-24 2025-12-11 Defuse Technologies, LLC Desensitized fertilizer compositions and methods of making same

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CN1034009C (zh) * 1994-07-13 1997-02-12 西安近代化学研究所 硝酸铵用防结块剂
FI108347B (fi) * 2000-01-04 2002-01-15 Kemira Agro Oy Menetelmõ ammoniumnitraatin stabiloimiseksi
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WO2017108801A1 (fr) 2017-06-29
CO2018007547A2 (es) 2018-07-31
US20180370864A1 (en) 2018-12-27
CN108698948A (zh) 2018-10-23

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